Process for coloring products of high molecular weight with pigments

ABSTRACT

DIBENZARHRONE SULFONAMIDES OR ISODIBENZANTHRONE SULFONAMIDES ARE USEFUL FOR COLORING HIGH-MOLECULAR ORGANIC PRODUCTS IN VOILET SHADES HAVING EXCELLENT FASTNESS PROPERTIES.

United States Patent 3,814,726 PROCESS FOR COLORING PRODUCTS MOLECULARWEIGHT WITH PIGMENTS Paul Hugelshofer and Fritz Kugler, Muttenz,Switzerland, assignors to Ciba-Geigy AG, Basel, Switzerland N Drawing.Continuation of application Ser. No. 98,115,

Dec. 14, 1970, which is a continuation-in-part of apphcation Ser. No.760,082, Sept. 16, 1968, both now abandoned. This application June 1,1972, Ser. No. 258,641

Int. 'Cl. C08f 45/14,- C09b 3/30 US. Cl. 26042.21 3 Claims ABSTRACT OFTHE DISCLOSURE Dibenzanthrone sulfonamides or isodibenzanthronesulfonamides are useful for coloring high-molecular organic products inviolet shades having excellent fastness properties.

CROSS-REFERENCES TO RELATED APPLICATIONS This is a continuation of Ser.No. 98,115 filed Dec. 14, 1970 and now abandoned which is acontinuation-in-part of Ser. No. 760,082 filed Sept. 16, 1968 and nowabandoned.

Violet pigments are very important, espeically for shadingcopperphthalocyanines. Hitherto, the products mainly available have beendioxazine pigments and isodibenzanthrone and the halogenation productsthereof. Although some special dioxazine pigments go a long way towardssatisfying the high demands made on fastness properties at the presenttime, they have the disadvantage that they are not sufficiently stabletowards flocculation in lacquers; furthermore, their price imposes alimit on their wider application. Although isodibenzanthrone and thehalogenation products thereof are advantageous in respect of price andshow good resistance to flocculation in lacquers, they are notsufficiently fast to migration for many purposes. (see for ex. Journalof the Oil and Color Chemists Ass. 46, pages 23-24 (1963).

The present invention invention is based on the surprising observationthat dibenzanthrones and isodibenzanthrones containing sulphonamidegroups are economic pigments possessing excellent fastness to light andmigration and which, compared with the dioxazines, display greatlyimproved resistance to flocculation. Thus, the advantages of the twoclasses of pigment mentioned above are combined in these products.

The pigments to be used in accordance with the invention preferablycorrespond to the formula or men 3,814,726 Patented June 4, 1974 2 inwhich one of the symbols X represents a carbonyl group and the otherrepresents a direct bond, Y represents'a halogen atom, m represents aninteger within the range of from 1 to 3 and n represents an integerwithin the range of from 1 to 5. Such compounds are known and may beobtained, for example,by the process described in Example 8 of BritishPatent Specification No. 807,224 in which isodibenzanthrone ordibenzanthrone is treated with chlorosulphonic acid and thesulphochloride so obtained is reacted with ammonia.

Mixtures of monosulphonamides and disulphonamides are generallyobtained, the latter preferably slightly predominating, corresponding toa mean sulphonamide content of 1.5 to 1.8. The pigments may also contain1 to 4, preferably 1 or 2, halogen atoms. The introduction of thehalogen atoms may be effected either prior to or subsequent to theintroduction of the sulphonamide groups.

The following are given as examples of materials to be colored inaccordance with the process of the present invention; plastic materials,for example, rubber and case in; polymerization resins, for example,polyvinyl chloride and the copolymers thereof, polyvinyl acetals,polyolefins, for example, polyethylene, polypropylene and polystyreneand copolymers thereof with polyesters derived from unsaturateddicarboxylic acids and diols, polyacrylates and the copolymers thereof,silicones and silicone resins. The pigments to be used in accordancewith the invention are also suitable for use in the preparation ofcolored condensation resins, for example, polyamides and especiallyaminoplasts, for example, urea-formaldehyde or melamine-formaldehyderesins, polyaddition resins, for example, epoxy or polyurethane resinsor alkyd resins, and they are also suitable for use in the preparationof colored lacquers containing one or more of the said resins in anorganic solvent, for example lacquers from nitro cellulose acrylicresin, alkyd-melamine resin, silicon resin, epoxide resin or chlorinatedrubber, or aqueous emulsions containing one or more of the said resinsor precondensates, if necessary, in the presence of organic solvents,for example, an oil-in water or a water-in oil emulsion. Such emulsionsare specially suitable for impregnating or printing textile materials orother sheet-like materials, for example, paper, leather and glass fibrefabrics, if necessary, with subsequent curing by a heat treatment. Thepigments to be used in accordance with the process of the invention mayalso be applied in the production of spuncolored fibres, for example,fibres made from viscose, cellulose esters, polyesters orpolyacrylonitrile. It may also be used with advantage in the preparationof printing incs.

The pigments to be used in accordance with the process of the invention,which are obtained from the synthesizing process in a physically usableform, are advantageously converted into a state of fine division priorto application, for example, by grinding in a dry or water-moist statein the presence or absence of an organic solvent and/ or a salt that canbe Washed out. I ,v

The pigments to be used in accordance with the process of the inventionmay be used in the pure form as socalled toners or in the form ofpreparation's'in which the pigment is present in a state of finedivision, for example, in a particle size not exceeding 3p. Suchpreparations may contain the usual additives, for example, dispersingagents or binders, and may be produced in a manner known pr se by anintensive mechanical treatment, for example, on a roller mill or in asuitable type of kneading-apparatus. The choice, of a dispersing mediumwhich permits intensive processing depends on the kind of preparation tobe produced. For example, sulphite cellulose waste liquor or salts ofdinaphthylmethane disulphonic acid may be used in the production ofaqueous, dispersible preparations and cellulose acetate mixed with asmall amount of solvent may be used for preparations employed in-thespinning of' cellulose acetate rayon.

By virtue of their chemical iriertness and good thermal stability, thepigmentscan generally be dispersed easily in the compositions orpreparations of the type mentioned, advantageously at some stage beforethey have been processed to their final form. The final processingoperations,

for exalmple, spinning, moulding, curing, casting, bonding Example 1 5parts of the pigment of the formula (S:NH2) 1,1 I

are mixed with 95 parts of dioctyl phthalate, and the mixture is groundin a ball mill until the pigment particles are smaller than 3p.

0.8 part of this dioctyl phthalate paste is then mixed with 13 parts ofpolyvinyl chloride, 7 parts of dioctyl phthalate, 0.1 part of cadmiumstearate and 1 part of titanium dioxide, and the mixture so obtained isworked to and fro for minutes on a two-roller mill at 140 C. A violetcoloration possessing very good fastness to light and migration isobtained.

The pigment used in this Example may be prepared in the followingmanner:

11.4 parts of isodibenzanthrone are introduced at room temperature (15to 25 C.) into 210 parts of chlorosulphonic acid, whereupon a greensolution forms. 6 parts of thionyl chloride are added to this solution,the reaction mixture is heated to 80 C. and then stirred for 2 hours at80 to 85 C. (internal temperature). The reaction mixture is then cooledto approximately C. and carefully discharged on to a mixture of 2,200parts of ice and 800 parts of water. The sulphochloride whichprecipitates is isolated by suction filtration and washed free frommineral acid with cold water (until the pH of the washing water is about3 to 4). The moist sulphochloride filter cake is suspended in 350 partsof 24% aqueous ammonia at 10 to C., the suspension is cooled to 0 C.,stirred for 2 hours at 0 to 5 C., then for 14 hours at room temperature15 to 25 C.) and finally for 1 hour at 50 to 60 C. The reaction mixtureis suction-filtered while warm and the filter residue is washed with hotwater until the filtrate runs colorless and neutral. The filter residueis then covered several times with hot alcohol and dried in vacuo at 50to 60 C. 15 parts of a mixture are obtained which consists ofapproximately equal parts of isodibenzanthrone monosulphonamide andisodibenzanthrone disulphonamide.

Example 2 40 parts of a nitrocellulose lacquer, 2.375 parts of titaniumdioxide and 0.125 part of'the pigment mentioned in the first paragraphof Example l are ground in a rod mill for 16 hours. A thin coating ofthe lacquer so obtained is applied to aluminum foil. "A violet coatinpos- 'sessing very good properties of fastness is obtained.

Example 3 tioned in the first paragraph of Example 1, '25 parts of 4celluloseacetate (54.5% combined acetic acid), 100 parts of sodiumchloride and 50 parts of diacetone alcohol is treated in a kneader, withcooling, until the pigment has the fine particle size required; 25 partsof water are then added and kneading is' continued until afine-grainedmass is obtained. The mass is then transferred to a suction filter andthe sodium chloride and diacetone alcohol arewashed out completely withwater. The batch is dried in a vacuum cabinet at C. and ground in ahammer mill. V

1.33 parts of the pigment preparation so obtained are added to anacetate rayon spinning composition consisting of parts ofcellulose'acetate and 376 parts of acetone. The batch is stirred for 3hours, which is sufficient to ensure complete dispersion of the pigment.The dope so obtained is spun into a filament inthe usual manner by thedry-spinning process. The filament displays a violet coloration whichpossesses very good fastness to light, washing and hypochlorite.

Example 4 0.25 part of the pigment mentioned in the first paragraph ofExample 1, 40 parts of an alkyd-melamine stoving lacquer having a 50%solids content, and 4.75 parts of titanium dioxide are ground for 24hours in a rod mill. A thin coating of the lacquer so obtained isapplied to aluminium foil and stoved for one hour at C. A violet coatingpossessing good fastness to light is obtained.

Example 5 4.8 parts of the pigment mentioned in the first paragraph ofExample 1 and 4.8 parts of the sodium salt of 1,1'-dinaphthylmethane 2,2disulphonic acid and 22.1 parts of water are ground in 'a colloid millof known design until all the pigment particles are smaller than 1;. Thepigment suspension so obtained has a pigment content of about 15%.

The aqueous suspension so obtained is added to a viscose spinningsolution and a violet-colored cellulose filament is spun therefrom bythe usual process. The coloration displays good fastness to light andhypochlorite.

Example 6 A dyebath is prepared containing per 1,000 parts of water, 15parts of a copolymer latex prepared fromv 85.8 parts ofisobutylacrylate, 9.6 parts of acrylonitrile and 4.6 parts of acrylicacid, 15 parts of a'70% emulsion of a methylolmelamineallylethermodified with soya fatty acid and emulsified with sulphonated castoroil, 50 parts of a water-soluble methyl ether of a urea-formaldehydecondensation product containing, per mol of urea, more than 2 mols offormaldehyde incorporated by condensation, 5 parts of the pigmentsuspension obtained in the manner described in the first paragraph ofExample 5, and 20 parts of 10% formic acid.

A dry cotton fabric is padded at room temperature with the abovedye-liquor to a liquor uptake of 65 to 80%, dried in the normal manner,if necessary, under tension (clip stenter or pin stenter) and then curedfor 5 minutes at to C. A violet dyeing possessing good properties offastness is obtained.

Example 7 100 parts of the pigment mentioned in the first paragraph ofExample 1, 40 parts of the product obtained by additively combining 15mols of ethylene oxide with 1 mol of ditertiary-butyl-para-cresol and 20parts of water are mixed in a kneading apparatus v to form a viscous,homogeneous dough. Kneading is carried out until the pigmentagglomerates which form on drying are uniformly and finely dispersed.The dough is carefully diluted with 90 parts of water while continuingthe kneading process and then homogenized by means of a cone mill orsome other suitable apparatus in a manner such that a viscous,homogeneous paste is formed which contains dispersed pigment primaryparticles virtually all of which have a oil-in-water'emulsion containing55% of petroleum hydroca'rbons, of'a' styrene butadiene emulsioncopolymer and 3.5% of a solutioncomprising about 75% by weight ofa'water-insoluble melamine-formaldehyde prima'ry condensate modifiedwith n'-butanol and about 25% by weight of r -butanol as separate innerphases and 36.5% of an'aqueous 'sblution containing 7.5 parts by weightof a non-ionic emulsifier prepared in accordance wtih Example 3 of U.S.Pat. No. 2,946,767, filed July 26, 1960 by Hans Gassmann per 92.5 partsby weight of water as outer phase, 80 parts of water and parts ofammonium nitrate, totalling 1,000 parts, to form a homogeneous, viscouspaste.

Fabrics made of natural or regenerated cellulose or synthetic fibers ofall kinds may be printed with this paste, application being effected inthe usual manner by means of rollers or screens. After drying at roomtemperature or at an elevated temperature and a subsequent heattreatment for a few minutes at 120 to 150 C., a violet print possessingexcellent fastuess to rubbing, washing and light is obtained.

Example 8 A mixture comprising 50 parts of the pigment mentioned in thefirst paragraph of Example 1, 100 parts of Staybelite Ester 10 (glycerolester of hydrogenated colo- 'ph0ny), 200 parts of sodium chloride and 18parts of diacetone alcohol is treated in a kneader, while cooling, untilthe pigment has the fine particle size required. The sodium chloride andthe diacetone alcohol are then removed from the dough by theintroduction of water at 80 C. The dough itself remains intact. Thedough, which is free from salt and solvent, is completely dried byheating the kneader with steam, allowed to cool, and then pulverized inthe kneader.

The preparation so obtained may be used, for example, for coloringlacquers. When used for this purpose, the preparation is advantageouslypasted with a small amount of toluene and the paste so obtained is thenmixed with the lacquer.

Example 9 150 parts of the dry pigment mentioned in the first paragraphof Example 1, 300 parts of a 20% casein solution, 40 parts of adispersing agent and 250 parts of distilled water are ground in asuitable device until most of the pigment particles measure less than-1,u.. The pigment paste so obtained is mixed with 50 parts of a 30% waxemulsion and a further 200 parts of a 20% casein solution and themixture is stirred to produce a homogeneous pigment paste. 50 parts ofthe 15'% pigment preparation so obtained are well mixed with 100 partsof a casein solution, 5 parts of sodium sulphoricinoleate, 50 parts of a10% egg albumin solution and 870 parts of distilled water.

The pigment dispersion so obtained which is ready for use is applied inone or two coats to dyed full-chrome grain leather by means of a plushpad or a brush. A levelling coat of the same pigment dispersion is thensprayed on under a pressure of 4 to 5 atmospheres. A 20% casein.

solution is then applied in the same manner, dried for a short periodand then hardened with 8 to 10% formaldehyde solution. The applicationof the pigment is concluded by machine glazing and hydraulic pressing at60 to 80 C. under a pressure of 150 to 200 atmospheres. The colorationdisplays good fastuess to light, excellent fastuess to wet rubbing and ahigh degree of transparency.

Example 10 '1 part of the pigment mentioned in the first paragraph ofExample 1 is mixed with 99 parts of high-pressure polyethylene and themixture is worked to and fro for 10 minutes on a roller mill at 140 to170 C. A violet film possessing excellentfastness' to light andmigration Example I 1 The following layers are prepared for use in themanufacture of laminated sheet material:

. (a) Strong paper made from unbleached sulphate cellulose (so-calledKraft paper) is saturated with an aqueous phenol-formaldehyde resinsolution, squeezed and dried.

(b) Paper made from pure, chemically bleached cellulose and containingzinc sulphide or titanium dioxide as filler as saturated with a 50%aqueous solution of dimethylolmelamine, squeezed and dried at C.

(c) 400 parts of decorative paper made from bleached cellulose andcontaining zinc suphide or titanium dioxide as filler are ground in aheater in 10,000 parts of water. 30 parts of the pigment suspensionobtained in the manner described in Example 5 are added to the pulp soobtained. The pigment is fixed by the addition of 16 parts of aluminiumsulphate. The colored decorative paper is saturated with a 50% aqueoussolution of dimethylolmelamine, squeezed, and then dried at 100 C.

((1) Depending on the quality of laminate required, the decorative paperis protected with tissue paper made of bleached special cellulose whichWeighs 40 grams per square meter. The tissue paper is also saturatedwith a 50% aqueous solution of dimethylolmelamine, squeezed, and thendried at 100 C.

Equal-sized pieces of the material so prepared, for example, measuring2.75 meters x 1.25 meters, are then placed one upon the other in thefollowing order: first, 3 to 5 sheets of paper (a), one sheet of paper(b), one sheet of paper (0) and, if desired or required, one sheet ofpaper (d). The whole assembly is then compressed between high-glosschromium-plated plates for 12 minutes at to C. under a pressure of 100kg. per square centimeter. The press is cooled to 30 C. and thecomposite material so formed is removed. It is colored violet on oneside and the coloration has good fastuess to light.

Example 12 130 parts of an aqueous pigment paste of a mixture ofisodiberrzanthrone monoand disulphonamide (moist press-cake, obtained inaccordance with Example 1) having a pigment content of 27% and 34 partsof behenic acid are treated in a kneader for 15 minutes at 60 C. Thewater that separates is decanted. 2.9 parts of magnesium hydroxide areadded and kneading is continued at 100 C.; the water which formsevaporates. When the whole has been homogeneously mixed, the productobtained is ground. A preparation containing 50% of pigment is obtainedin the form of a fine powder. 4

1 part of the preparation so obtained is mixed with 100 parts ofpolypropylene and the mixture is stirred for 45 minutes at 280 C. in anitrogen atmosphere. When the melt is extruded through a die, a polypropylene strip colored a bluish violet is obtained. When the strip is coolit can be granulated and the granules may be used for injectionmoulding.

Example 13 Two mixtures are prepared, each comprising 1 part of thepigment preparation obtained in accordance with Example 12 and 100 partsof polystyrene. One mixture is stirred for 45 minutes at 280 C. and theother for 15 minutes at 300 C., stirring being carried out in a nitrogenatmosphere in each case. When the melts are extruded through a die,bluish violet polystyrene strips are obtained which, when cool, can begranulated and the granules may be used for injection moulding.

E 4;1- I 1 part of the finely divide d pigment' mentioned: in Example 1is added to a solution of 165 parts of polysew/2s acrylonitrile in 834partsof dimethylformamide. The

99 parts of a polyamide made from e-caprolactam in the form of chips arecoated with one part of the finely divided pigment mentioned in Example1 in the form of a dry powder. The powdered chips are spun in the usualmanner, for example, by the grid-spinning process, at about 290 to 295C. The filament so obtained has a bluish violet coloration whichpossesses good fastness to light and wet treatments.

Example 16 99 parts of polyethylene terephthalate chips are coated withone part of the finely divided pigment mentioned in Example 1 in theform of a dry powder, and then melted and spun in the usual manner. Thepolyester filament so obtained has a bluish violet coloration whichdisplays outstanding properties of fastness.

Example 17 A reddish blue coloration is obtained when theisodibenzanthrene sulphonamide used in the preceding Examples isreplaced by a dibenzanthrone sulphonamide.

The pigment may be obtained in the following manner: 11.4 parts ofdibenzanthrone are introduced at room temperature into 210 parts ofchlorosulphonic acid, whereupon a reddish violet solution forms. 6 partsof thionyl chloride are added to the solution, the reaction mixture isheated to 70 C. and then stirred for 2 hours at that temperature. Thereaction mixture is then cooled to 10 C. and carefully discharged on toa mixture of 2,200 parts of ice and 800 parts of water. Thesulphochloride which precipitates is isolated by suction filtration andwashed with cold water until the washings have a pH of 4. The

moist filter cake is suspended in 350 parts of 24% aqueous ammonia at 10to 15 C., the suspension is cooled to C. and then stirred, first for 2hours at 0 to C., then for 15 hours at room temperature and finally forone hour at 50 to 60 C. The reaction mixture is then suctionfilteredwhile warm and the filter residue is washed with hot ammoniacal wateruntil the washings run colorless. The filter residue is then washed withhot water until the washings run neutral and finally covered with hotalcohol. The residue is dried in vacuo at 60 to 70 C. 14.5 parts of amixture of dibenzanthrone monoand disulphonamide having a meansulphonamide group content of 1.55 to 1.60 groups per molecule areobtained.

Example 18 A bluish red coloration is obtained when the pigment used inExamples 1 to 16 is a dichloro-isodibenzanthrone sulphonamide.

The pigment may be obtained in the following manner:

13.1 parts of dichloroisodibenzanthrone are introduced at isolated bysuction filtrationv and washed with cold water until the washings have apH of 4. The moist sulphochloride filter cake is suspended in 350 partsof 24% aqueous ammonia at to C., the suspension is cooled to 0 i to 5their stirredfor 2 liours 'atthat temperature, then for;.l6.;hours,atroomitemperature and'ffin'ally for one hour. at 60. C.--'I?he reactionmixture. is suction-filtered whilewarm and the filterresidue is washedwith hot am- .moniacal water until. the filtrate; runs colorless. Thefilter Example 19 A reddish violet coloration is obtained when thepigment obtained in the manner described below is used in Examples 1 to16.

11.4 parts of isodibenzanthroneare introduced at room temperature into210 parts of chlorosulphonic acid. 6 parts of thionyl chloride areadded, the reaction mixture is heated to C. and stirred for '2 hours atthat temperature. The temperature is raised to C., a few grains ofiodine are added to the reaction mixture and then 4.0 parts of bromineare added dropwise within 2 hours. After a further 2 hours, the reactionmixture is cooled to 10 C. and then carefully discharged on to a mixtureof 1,500 parts of ice and. 500 parts of water. The sulphochloride whichprecipitates is isolated by suction filtration and the filter residue iswashed free from mineral acid with cold water until the washings have apH of 4. The moist filter cake is suspended in 350 parts of 24% aqueousammonia, the suspension is cooled to 0 C., stirred for 2 hours at 0 to 5C., then for 16 hours at room temperature and finally forone hour at 60C. The reaction mixture is suction-filtered, and the filter residue iswashed with hot alkaline water until the filtrate runs colorless. Thefilter. residue is then washed with hot water until the washings runrieutral, covered several times with hot alcohol and thendried inv'a'cuo at 60 to 70 C. 16.5 parts of a mixture? of halogenatedisodibenzanthrone monoand disulphonamides are obtained, which mixturehas a sulphonamide group content .of 1.8 groups per molecule, a chlorinecontent of 3.7% and 'a bromine content of 22.9%, which corresponds to anaverage of 0.79 chlorine atoms and 2.19 bromine atoms per molecule.

Example 20 A reddish blue coloration is obtained when the pigmentobtained in the manner described below is used in Examples 1 to 16. I I

11.4 parts of dibenzanthrone are introduced at room temperature into 210parts of chlorosulphonic acid. 6 parts of thionyl chloride are added tothis solution and the reaction mixture is heated to 85 C. and stirredfor 2 hours at that temperature. Afew grains of iodine are added andthen 3.5 grams of chlorine are introduced within 1% hours, thetemperature being kept at 85 C. The reaction mixture is then cooled andcarefully discharged on to a mixture of 1,500 parts of ice and 500 partsof water. The sulphochloride which precipitates is isolated by suctionfiltration and then washed with cold water until the washings have a pHof 4. The moist filter cake is then suspended in 350 ml. of 24% aqueousammonia. The suspension is then stirred for 2 hoursat 0 to 5 C.,- for 15hour-sat room temperature and finally for on'e'hour at-60"C.'Thereaction mixture is filtered,

the filter. residue is washed with hot ammoniacal water'until'tliewashings run colorless and then with hot water until-thewashings show a neutral-reaction. The residue is covered several-timeswith hot alcohol and then dried in vacuo at 60 to 70 C. 8.3v parts of amixture of chlorinated dibenzanthrone monoand disulphonamide areobtained, which mixture has a mean sulphonamide group content of 1.8groups per molecule anda chlorine content of 5% which corresponds to 0.9chlorine atoms per molecule.

3,814,726 9 10 Example 21 solvent mixture during 35 minutes at roomtemperature in i heel stirrer running at 3000 revolutions per minma alsobe obtained when a gear w the? ez t iizifi i i iil ma hner describedbelow is ute: Solvent mlxture: 10 Parts of Xylene 4 Pints of ethyl d igixam leg 1 to 16 ene glycol monoethyl ether, 4 parts of acetic acidbutyl 11.4 parts 5f. clibenzanthrone are introduced at room 5 ester 2Parts of nbutanol, 1 P of levelling agent and I 1 part of 1% siliconeoil solution in xylene. After comg u bi ihiori yi clfib id e aii afldz dib th ig l biio ii fig P te fine dlstributlon the binder solutions areadded with reaction mixture is heated toss, C and Stirred at thatfurther stirring: 23.5 parts of Cardura 30, 80% in xylene (Shell), 25.0parts of Alkydal F 25, 75% in xylene igo ia gtg g g f gfg gg ggf g if:if: (Bayer) and 21.5 parts of Cibamin H 86, 75% in butanol (CIBA). Afterstirring for minutes the lacquer is parts of brom ne are added dropwisewithin one hour and d th thev batch .is istirred for a further 2 hoursat 100 C. The e usual manner and cured for 30 minutes atreaction-mixture is then cooled to 10 C. and discharged The preparationsobtained according to Examples 240 carefully on to a mixtureof 1,500parts of ice and 500 can be e 1 A, 15 mp oyed instead of the preparationobtained acparts of water. The sulphochlorlde which preclpitates 1scording to Example 1 with equally good results isolated by suctionfiltration and washed free from mineral acid with cold water until thewashings have a pH of 4. The moist filtencake is suspended in 350 ml. of24% q p f ammonia imdihe Suspension is stirred for 2 hours 8 parts of apigment preparation obtained according to at 0 to 5? C then for 15 hoursat room tefnperaiure 20 Example 5 are distributed in 22 parts of asolvent mix Y f I 0116 r6 Thc reactlon mlxfure 1s ture consisting of 10parts of xylene, 8 parts of acetic acid suctionfiltered and the residueis washed Wlth hot but l t r and 2 parts of cyclohexanone during mina wiWater until the washings run c0101 less and then utes at roomtemperature in a gear wheel stirrer running with hot water until thewashings show a neutral reaction. at 3000 revolutions minute.

The filter residue is then covered several times with hot 25 Aftoompiote fi ib i a bi d l i alcohol andthen dried in vacuo at 60 to 70C. 13.7 parts sistiog f 5 parts f Silicone rosin UD 16o (Bayer), of amixture halOgeIlated dibenzamhl'one monoand 75 in xylene/butanol 8:2, 1part of polymeric butyl disulphonamide are obtained, which mixture has amean titanato and 05 part of lead naphthenate containing sulphonamidegroup content of 1.85 groups per molecule, of lead i added with f thstirring a chlorine content of 3.1%, corresponding to 0. 64 chlo- 30 Aftstirring 15 minutes the lacquer is applied in Example 24 (silicone resinlacquer) rine atoms per molecule, and a bromine content of 14.8%, theusual manner or by the coil coating process and is corresponding to1.3-6 bromine atoms per molecule. SGGS cured f 30 minutes at 200 C of Mesieg 1 P Of Cellulose acetoblltyrate and The preparations obtainedaccording to Examples 1-4 0.3'part of diacetone-alcohol. and 6l0 can beemployed instead of the preparation ob- .The. resulting kneaded mass isdecomposed by adding 1 part of 25% aqueous sodium chloride solution,granulat dpa W0rked-11P as inExample Example 25 (epoxide resin lacquer)Example 22 (acrylic resin stoving lacquer) tained according to Example 5with equally good results.

I I I 40 5.0 parts of the pigment preparation obtained according 8 partsof the preparation obtained according to Examto Example 1 aredistributed in 23.0 parts of a solvent ple 31 are stirred into 20 partsof solvent of the following mixture consisting of 3.0 parts ofn-propanol, 6.0 parts of composition: 50 parts of Solvesso-150, 15 partsof butyl ethylene glycol monoethyl ether, 6.0 parts of ethylene acetate,5 parts of Exkin II (levelling agent), 25 parts of glycol ethyl etheracetate and 8.0 parts of xylene in the methyl isobutyl ketone and 5parts of silicone oil (1% in same manner as in Example 12.

Solvesso 150). After complete fine distribution has been 53.2 parts of abinder solution I consisting of: 21.3 achieved (in about 15-60 minutesdepending on the parts of Araldite 6097 (CIBA), 14.4 parts ofdiacetonenature, of the stirrer) the binders are added, namely 48.3alcohol, 3.2 parts of o-dichlorobenzene and 14.3 parts of partsofBaycryl L530 (51% in xylene/butanol, 3:1) and xylene, as well as 18.8parts of binder solution H consist- 23.7 parts of Maprenal TI'X (55% inbutanol). After ing of a solution of 75% of Cibamin H 53 (CIBA) in briefhomogenisation the lacquer is applied according to butanol are addedwith further stirring.

usual methods for example spraying and dipping or After stirring for 15minutes the lacquer is applied in especially, for the continuous coatingof sheet metal, by the usual manner and cured for 30 minutes at 180 C.the coil coating process, and is stoved (stoving 30 min- Thepreparations obtained according to Examples 2-10 utes,;130 C.). Theresulting blue lacquerings are distin- 55 can be used instead of thepreparation obtained according guished by very good levelling, highgloss and excellent o Example 1 with equally good results.

fine distribution of the pigment as well as by excellent We claim:

resistance to weathering. 1. Polyvinyl chloride in which a pigment ofthe formula The preparations obtained according to Examples 2-10 isincorporated, in which one of the symbols X represents canbe employedinstead of the preparation obtained aca carbonyl group and the otherrepresents a directbond, cordingto Example 1 with equally good results..Y represents a halogen atom, m represents an integer within the rangeof from 1 to 3 and n represents an inte er -s i if zh g f mflamme islovmgdlacquez) within the range of from 1 to 5. g

par s o e plgmen preparation 0 taine accor ing" 2. Polyvinyl chloride asclaimed in claim l in wh'ch to' Example jl are distributed in 22 partsof the following pigment of the formula 1 a is incorporated, in which Xhas the meaning ascribed to 3. Polyvinyl chloride as claimed in claim 1which a it in claim 2, m stands for 1 0r 2 and n and u each reprepigmentof the formula sents an integer within the range of from 1 to 4, the sumis incorporated in which m is 1 or 2. of n and u being not greater than4.

References Cited UNITED STATES PATENTS FOREIGN PATENTS 807,224 1/1959Great Britain.

MORRIS LIEBMAN, Primary Examiner P. R. MICHL, Assistant Examiner US. Cl.X.R.

